1. Field of the Invention
The present invention relates to a catalyst, a method of making said catalyst and a process for polymerizing xcex1-olefins with said catalyst. The catalyst precursor is synthesized using metal alkoxides or metal dialkyls, a halogenating agent, an electron donor compound and a titanating agent. The catalyst precursor is activated with an aluminum alkyl and is used, optionally with a stereoselectivity control agent, to polymerize xcex1-olefins, particularly propylene.
2. Description of the Related Art
Ziegler-Natta catalysts, their general methods of making, and subsequent use for polymerization of olefins, are well known in the art. However, while much is known about Ziegler-Natta catalysts, improvements in catalyst performance and in their ability to produce polyolefins having certain properties are desirable.
U.S. Pat. No. 4,472,521, issued Sep. 18, 1984 to Band, discloses a polyolefin catalyst made by contacting a Mg(OR)2 and/or Mn(OR)2 with titanium tetrachloride, then with a titanium tetrachloride halogenating agent, and then with an electron donor.
U.S. Pat. No. 4,673,661, issued Jun. 16, 1987, and U.S. Pat. No. 4,724,255, issued Feb. 9, 1988, both to Lofgren et al. disclose a polyolefin catalyst component made by chlorinating a magnesium alkyl which is then contacted with titanium tetrachloride, a Lewis base, and then at least once with titanium tetrachloride in the absence of a Lewis base. Lofgren et al. teach the criticality of an electron donor at the first titanium tetrachloride treatment step and further teach that away from the presence of an electron donor at subsequent titanation steps.
U.S. Pat. No. 4,855,271, issued Aug. 8, 1989, and U.S. Pat. No. 4,937,300, both to McDaniel et al. disclose a polyolefin catalyst derived from alumina impregnated with magnesium alkoxide, which is subsequently contacted with a lower order alcohol, chlorinated with silicon tetrachloride, and subsequently etched with a titanium tetrachloride.
U.S. Pat. No. 5,075,270, issued Dec. 24, 1991 to Brun et al. discloses a polyolefin catalyst made by reacting a magnesium alkoxide with an aluminosiloxane derivative, which product is then chlorinated with silicone tetrachloride, followed by transition metal treatment with titanium tetrachloride, with an electron donor optionally associated with the transition metal.
Even with these prior art methods there is another need for polyolefin catalysts having improved performance. These and other needs in the art will become apparent to those of skill in the art upon review of this patent specification.
It is one object of the present invention to provide for improved polyolefin catalysts, methods of their making, and methods of polymerizing olefins, particularly propylene.
It is another object of the present invention to provide for polyolefin catalysts having improved performance.
These and other objects of the present invention will become apparent to those of skill in the art upon review of this patent specification.
According to one embodiment of the present invention there is provided a process for preparing a polyolefin catalyst precursor. The method first includes contacting a metal alkoxide, such as magnesium ethoxide, or a metal dialkyl with a halogenating agent, such as titanium tetrachloride, to form (A) an alkoxy metal halide (or an alkyl metal halide), metal dihalide and complexes thereof. These compounds and complexes are formed in a slurry with a hydrocarbon solvent. An electron donor, such as an alkyl phthalate compound, was added and the mixture was heated. The slurry was cooled and the solid separated and washed. The solid was again treated with titanium tetrachloride in a slurry and heated. The solid was separated, washed and dried.
The method of the present invention for making a catalyst component generally includes the steps of halogenating a metal alkoxide, metal dialkyl or metal alkoxyhalide, introducing an electron donor which is then followed by at least one subsequent titanation treatment.
Metal alkoxides, metal dialkyls or metal alkoxyhalides suitable for use in the present invention include any that which when utilized in the present invention will yield a suitable polyolefin catalyst. Preferred metal alkoxides, metal dialkyls and metal alkoxyhalides include those with metal from Group IIA and VIIB. Metal alkoxide, metal dialkyls and metal alkoxyhalides are preferred in that order. Most preferred is a magnesium alkoxide.
The general formula of the metal alkoxide, metal dialkyl or metal alkoxyhalide is M(OR)2, MR2 M(OR)X, wherein M is any suitable metal, and R is a hydrocarbyl or substituted hydrocarbyl moiety having from 1 to 20 carbon atoms and X is a halogen. M is preferably a Group IIA and VIIB metal, most preferably magnesium; R is preferably a hydrocarbyl or substituted hydrocarbyl moiety having from 2 to 10 carbon atoms, and more preferably R is a hydrocarbyl or substituted hydrocarbyl moiety having from 2 to 6 carbon atoms, and most preferably, R has from 2 to 4 carbon atoms. X is preferably chlorine.
Examples of preferred species of metal alkoxides include magnesium ethoxide, magnesium butoxide, manganese ethoxide, and manganese butoxide. The most preferred metal alkoxide species is magnesium ethoxide. While not required, it is preferred that the magnesium alkyls be soluble in a hydrocarbon solvent. Examples of suitable magnesium dialkyls include dibutyl magnesium and butylethyl magnesium.
Halogenating agents are those compounds which can cause replacement of the alkoxide group(s) or the alkyl groups with a halogen. Halogenating agents useful in the halogenating step for halogenating the metal alkoxide, metal dialkyl or metal alkoxyhalide include any halogenating agent which when utilized in the present invention will yield a suitable polyolefin catalyst. Chlorides are the preferred halogenating agents.
Group III, Group IV and Group V halides may be employed, as may hydrogen halides, or the halogens themselves. Specific examples of preferred halogenating agents are BCl3, AlCl3, CCl4, SiCl4, TiCl4, ZrCl4, VOCl4, VO2Cl, CrO2Cl, SbCl5, POCl2, PCl5, and HfCl4. More preferred halogenating agents are SiCl4 and TiCl4, with the most preferred halogenating agent being TiCl4. Other halogenating agents include alkyl halo silanes of the formula RxSiX(4xe2x88x92x), wherein X is a halogen, R is a substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms, and X is a halogen.
This initial halogenating of the metal alkoxide or metal dialkyl compound is generally conducted in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. The preferred solvents are toluene and heptane.
In this halogenating step, the mole ratio of metal alkoxide or metal dialkyl to halogenating agent is generally in the range of about 6:1 to about 1:3, preferably in the range of about 3:1 to about 1:2, and more preferably in the range of about 2:1 to about 1:2.
This initial halogenating step is generally carried out at a temperature in the range of about 0xc2x0 C. to about 100xc2x0 C., a pressure in the range of about 15 psi to about 50 psi, and for a reaction time in the range of about 0.5 to about 4 hours. Preferably, the halogenating step is carried out at a temperature in the range of about 20xc2x0 C. to about 90xc2x0 C., a pressure in the range of about 15 psi to about 30 psi, and for a reaction time in the range of about 1 hour to about 2 hours.
Once the halogenating step is carried out and the metal alkoxide, metal dialkyl or metal alkoxyhalide is halogenated,the precipitated solid halide product is recovered by any suitable method, and washed with a hydrocarbon solvent to remove any reactants from the halogenating step.
An internal electron donor is then added to the metal halide. Internal electron donors for use in the preparation of polyolefin catalysts are well known, and any suitable internal electron donor may be utilized in the present invention which will provide a suitable catalyst. Electron donors are Lewis bases and may be an organic compounds of oxygen, nitrogen, phosphorous, or sulfur which can donate an electron pair to the catalyst.
The electron donor may be a monofunctional or polyfunctional compound, advantageously selected from among the aliphatic or aromatic carboxylic acids and their alkyl esters, the aliphatic or cyclic ethers, ketones, vinyl esters, acryl derivatives, particularly alkyl acrylates or methacrylates and silanes. Preferably, the electron donor of the present invention is an alkyl phthalate, and, more preferably, is a dialkyl phthalate. Specific examples of a suitable electron donor are diethyl phthalate (DEP) and di-isobutyl phthalate (DIBP). The amount of electron donor utilized will generally vary over the range of about 0.1 to about 1.0 mmol phthalate/g Mg(OEt)2, preferably from about 0.1 to 0.2 mmol phthalate/g Mg(OEt)2.
The contact time for addition of the electron donor ranges from about 0.5 hours to about 4 hours, preferably from about 1 hour to about 2 hours. Suitable temperatures for the addition of the electron donor step are generally in the range of about 20xc2x0 C. to about 90xc2x0 C., with suitable pressures in the range of about 15 psi to about 50 psi.
The titanation step is generally carried out by first slurrying the intermediate product. Nonlimiting examples of suitable hydrocarbons solvent include heptane, hexane, toluene, octane and the like.
The titanating agent is preferably a tetra-substituted titanium compound with all four substituents being the same and the substituents being a halide or an alkoxide or phenoxide with 2 to 10 carbon atoms. The same compound used as a halogenating agent may be used as a titanating agent. The most preferred titanating agent is TiCl4.
In general, the amount of titanium tetrachloride utilized will generally be in the range of about 0.5 to about 5 equivalents, preferably in the range of about 1 to about 4, and most preferably in the range about 1.5 to about 2.5 equivalents (based on the magnesium compound).
Following the addition of the titanium tetrachloride, the slurry is then further heated to a temperature in the range of about 90xc2x0 C. to about 150xc2x0 C., preferably to a temperature in the range of about 100xc2x0 C. to about 125xc2x0 C. The slurry is held in this elevated temperature for a holding period in the range of about 0.5 hours to about 8 hours, preferably for a holding period in the range of about 1 hour to about 4 hours. Subsequently, the solid precipitate is recovered by any suitable recovery technique and washed with a hydrocarbon solvent.
The method of using the catalyst component in the polymerization of olefins generally include combining the catalyst component with a cocatalyst to form an active catalyst, adding an external electron donor for stereoselectivity control, optionally prepolymerizing the catalyst with a small amount of monomer, introducing the catalyst into a polymerization reaction zone containing the monomer.
The cocatalyst component used to activate the catalyst component is an organoaluminum cocatalyst component to form a catalyst system suitable for the polymerization of olefins. Typically, the cocatalysts which are used together with the transition metal containing catalyst component are organometallic compounds of Group Ia, IIa, and IIIa metals, such as aluminum alkyls. The aluminum alkyl cocatalyst is of the general formula AlRxe2x80x23 where Rxe2x80x2 is an alkyl of from 1-8 carbon atoms or a halogen and Rxe2x80x2 may be the same or different with at least one R1 being an alkyl. Examples-of aluminum alkyls are trimethyl aluminum (TMA), triethyl aluminum (TEAl), triisobutyl aluminum (TiBAl) and diethyl aluminum chloride (DEAC). The preferred aluminum alkyl is TEAl.
External donors which may be utilized in the preparation of a catalyst according to the present invention include organosilane compounds such as alkoxysilanes of general formula SiRm(ORxe2x80x2)4xe2x88x92m where R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group; Rxe2x80x2 is an alkyl group; and m is 0-3, wherein R may be identical with Rxe2x80x2; when m is 0, 1 or 2, the Rxe2x80x2 groups may be identical or different; and when m is 2 or 3, the R groups may be identical or different
Preferably, the external donor of the present invention is selected from a silane compound of the following formula: 
wherein R1 and R4 are both an alkyl or cycloalkyl group containing a primary, secondary or tertiary carbon atom attached to the silicon, R1 and R4 being the same or different; R2 and R3 are alkyl or aryl groups. In a preferred embodiment, R1 is a alkyl or cycloalkyl of 1-6 carbon atoms, preferably methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl; R2 and R3 are methyl, ethyl, propyl, or butyl groups and not necessarily the same; and R4 is also a alkyl or cycloalkyl of 1-6 carbon atoms, preferably methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl. Specific external donors are cyclohexylmethyldimethoxy silane (CMDS), diisopropyldimethoxysilane (DIDS) cyclohexylisopropyl dimethoxysilane (CIDS), dicyclopentyldimethoxysilane (CPDS) or di-t-butyl dimethoxysilane (DTDS), the most preferred being CPDS.
Generally, a prepolymerization process is effected by contacting a small amount of monomer with the catalyst after the catalyst has been contacted with the electron donor. A pre-polymerization process is described in U.S. Pat. Nos. 4,767,735, 4,927,797 and 5,122,583, hereby incorporated by reference.
The catalysts of the present invention can be used for the polymerization of any type of xcex1-olefins. For example, the present catalyst is useful for catalyzing ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and other xcex1-alkenes having at least 2 carbon atoms, and also for mixtures thereof. Preferably, the catalysts of the present invention are utilized for the polymerization of propylene to produce polypropylene.